Aromatic transformation using UZM-44 aluminosilicate zeolite

ABSTRACT

A new family of aluminosilicate zeolites designated UZM-44 has been synthesized. These zeolites are represented by the empirical formula.
 
Na n M m   k+ T t Al 1-x E x Si y O z  
 
where “n” is the mole ratio of Na to (Al+E), M represents a metal or metals from zinc, Group 1, Group 2, Group 3 and or the lanthanide series of the periodic table, “m” is the mole ratio of M to (Al+E), “k” is the average charge of the metal or metals M, T is the organic structure directing agent or agents, and E is a framework element such as gallium. UZM-44 may be used to catalyze an aromatic transformation process by contacting a feed comprising at least a first aromatic with UZM-44 at hydrocarbon conversion conditions to produce at least a second aromatic.

CROSS REFERENCE TO RELATED APPLICATIONS

This application is a Division of copending application Ser. No.13/792,813 filed Mar. 11, 2013, which application claims priority fromProvisional Application 61/736,319, filed Dec. 12, 2012, now expired,the contents of which are hereby incorporated by reference in itsentirety.

FIELD OF THE INVENTION

This invention relates to a new family of aluminosilicate zeolitesdesignated UZM-44 as the catalytic composite for aromatic transformationreactions. They are represented by the empirical formula of:Na_(n)M_(m) ^(k+)T_(t)Al_(1-x)E_(x)Si_(y)O_(z)where M represents a metal or metals from zinc or Group 1 (IUPAC 1),Group 2 (IUPAC 2), Group 3 (IUPAC 3) or the lanthanide series of theperiodic table, T is the organic directing agent or agents derived fromreactants R and Q where R is an A,Ω-dihalosubstituted alkane such as1,5-dibromopentane and Q is at least one neutral amine having 6 or fewercarbon atoms such as 1-methylpyrrolidine. E is a framework element suchas gallium.

BACKGROUND OF THE INVENTION

Zeolites are crystalline aluminosilicate compositions which aremicroporous and which are formed from corner sharing AlO₂ and SiO₂tetrahedra. Numerous zeolites, both naturally occurring andsynthetically prepared, are used in various industrial processes.Synthetic zeolites are prepared via hydrothermal synthesis employingsuitable sources of Si, Al and structure directing agents such as alkalimetals, alkaline earth metals, amines, or organoammonium cations. Thestructure directing agents reside in the pores of the zeolite and arelargely responsible for the particular structure that is ultimatelyformed. These species balance the framework charge associated withaluminum and can also serve as space fillers. Zeolites are characterizedby having pore openings of uniform dimensions, having a significant ionexchange capacity, and being capable of reversibly desorbing an adsorbedphase which is dispersed throughout the internal voids of the crystalwithout significantly displacing any atoms which make up the permanentzeolite crystal structure. Zeolites can be used as catalysts forhydrocarbon conversion reactions, which can take place on outsidesurfaces as well as on internal surfaces within the pore.

A particular zeolite, IM-5, was first disclosed by Benazzi, et al. in1996 (FR96/12873; WO98/17581) who describe the synthesis of IM-5 fromthe flexible dicationic structure directing agent,1,5-bis(N-methylpyrrolidinium)pentane dibromide or1,6-bis(N-methylpyrrolidinium)hexane dibromide in the presence ofsodium. After the structure of IM-5 was solved by Baerlocher et al.(Science, 2007, 315, 113-6), the International Zeolite StructureCommission gave the code of IMF to this zeolite structure type, seeAtlas of Zeolite Framework Types. The IMF structure type was found tocontain three mutually orthogonal sets of channels in which each channelis defined by a 10-membered ring of tetrahedrally coordinated atoms,however, connectivity in the third dimension is interrupted every 2.5nm, therefore diffusion is somewhat limited. In addition, multipledifferent sizes of 10-membered ring channels exist in the structure.

Applicants have successfully prepared a new family of materialsdesignated UZM-44. The topology of the materials is similar to thatobserved for IM-5. The materials are prepared via the use of a mixtureof simple commercially available structure directing agents, such as1,5-dibromopentane and 1-methylpyrrolidine. UZM-44 may be used as acatalyst in aromatic transformation reactions.

SUMMARY OF THE INVENTION

As stated, the present invention relates to using a new catalyticcomposite comprising a new aluminosilicate zeolite designated UZM-44 ina process for aromatic transformation. Accordingly, one embodiment ofthe invention is a material having a three-dimensional framework of atleast AlO₂ and SiO₂ tetrahedral units and an empirical composition inthe as synthesized and anhydrous basis expressed by an empirical formulaof:Na_(n)M_(m) ^(k+)T_(t)Al_(1-x)E_(x)Si_(y)O_(z)where “n” is the mole ratio of Na to (Al+E) and has a value fromapproximately 0.05 to 0.5, M represents at least one metal selected fromthe group consisting of zinc, Group 1 (IUPAC 1), Group 2 (IUPAC 2),Group 3 (IUPAC 3), and the lanthanide series of the periodic table, andany combination thereof, “m” is the mole ratio of M to (Al+E) and has avalue from 0 to 0.5, “k” is the average charge of the metal or metals M,T is the organic structure directing agent or agents derived fromreactants R and Q where R is an A,Ω-dihalogen substituted alkane having5 carbon atoms and Q is at least one neutral monoamine having 6 or fewercarbon atoms, “t” is the mole ratio of N from the organic structuredirecting agent or agents to (Al+E) and has a value of from about 0.5 toabout 1.5, E is an element selected from the group consisting ofgallium, iron, boron and combinations thereof, “x” is the mole fractionof E and has a value from 0 to about 1.0, “y” is the mole ratio of Si to(Al+E) and varies from greater than 9 to about 25 and “z” is the moleratio of O to (Al+E) and has a value determined by the equation:z=(n+k·m+3+4·y)/2

Another embodiment of the catalytic composite of the invention is amicroporous crystalline zeolite having a three-dimensional framework ofat least AlO₂ and SiO₂ tetrahedral units and an empirical composition inthe as synthesized and anhydrous basis expressed by an empirical formulaof:Na_(n)M_(m) ^(k+)T_(t)Al_(1-x)E_(x)Si_(y)O_(z)where “n” is the mole ratio of Na to (Al+E) and has a value fromapproximately 0.05 to 0.5, M represents a metal or metals from Group 1(IUPAC 1), Group 2 (IUPAC 2), Group 3 (IUPAC 3), the lanthanide seriesof the periodic table or zinc, “m” is the mole ratio of M to (Al+E) andhas a value from 0 to 0.5, “k” is the average charge of the metal ormetals M, T is the organic structure directing agent or agents derivedfrom reactants R and Q where R is an A,Ω-dihalogen substituted alkanehaving 5 carbon atoms and Q is at least one neutral monoamine having 6or fewer carbon atoms, “t” is the mole ratio of N from the organicstructure directing agent or agents to (Al+E) and has a value of from0.5 to 1.5, E is an element selected from the group consisting ofgallium, iron, boron and combinations thereof, “x” is the mole fractionof E and has a value from 0 to about 1.0, “y” is the mole ratio of Si to(Al+E) and varies from greater than 9 to about 25 and “z” is the moleratio of O to (Al+E) and has a value determined by the equation:z=(n+k·m+3+4·y)/2and the zeolite is characterized in that it has the x-ray diffractionpattern having at least the d-spacings and intensities set forth inTable A. The zeolite is thermally stable up to a temperature of greaterthan 600° C. in one embodiment and at least 800° C. in anotherembodiment.

Another embodiment of the invention is a process for preparing thecrystalline microporous zeolite described above. The process comprisesforming a reaction mixture containing reactive sources of Na, R, Q, Al,Si and optionally E and/or M and heating the reaction mixture at atemperature of about 160° C. to about 180° C., or about 165° C. to about175° C., for a time sufficient to form the zeolite. The reaction mixturehas a composition expressed in terms of mole ratios of the oxides of:a-bNa₂O:bM_(n/2)O:cRO:dQ:1−eAl₂O₃ :eE₂O₃ :fSiO₂ :gH₂Owhere “a” has a value of about 10 to about 30, “b” has a value of 0 toabout 30, “c” has a value of about 1 to about 10, “d” has a value ofabout 2 to about 30, “e” has a value of 0 to about 1.0, “f” has a valueof about 30 to about 100, “g” has a value of about 100 to about 4000.With this number of reactive reagent sources, many orders of additioncan be envisioned. Typically, the aluminum reagent is dissolved in thesodium hydroxide prior to adding the silica reagents. Reagents R and Qcan be added together or separately in many different orders ofaddition.

Yet another embodiment of the invention is a hydrocarbon conversionprocess using the above-described zeolite. The process comprisescontacting the hydrocarbon with the zeolite at conversion conditions togive a converted hydrocarbon. Specifically, the zeolite is useful as thecatalytic composite in aromatic transformation reactions. At least afirst aromatic is contacted with the zeolite to produce at least asecond aromatic. One specific embodiment of the process is a process forproducing methylaromatics by contacting at least one C2-C6 alkane andbenzene with the UZM-44 zeolite to generate at least one methylatedaromatic. Examples of commercially important methylated aromaticsinclude toluene and xylenes. The reactions may involve cracking,aromatic alkylation, and transalkylation.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is an XRD pattern of the UZM-44 zeolite formed in Example 1. Thispattern shows the UZM-44 zeolite in the as-synthesized form.

FIG. 2 is also an XRD pattern of the UZM-44 zeolite formed in Example 1.This pattern shows the UZM-44 zeolite in the H⁺ form.

FIG. 3 is a plot derived from the N₂ BET experiment where dV/d log(D) isplotted against the pore diameter. This plot shows the incrementalamount of nitrogen adsorbed at each pore diameter measured.

DETAILED DESCRIPTION OF THE INVENTION

Applicants have prepared a catalytic component suitable for catalyzingaromatic transformation reactions where the catalytic component is analuminosilicate zeolite whose topological structure is related to IMF asdescribed in Atlas of Zeolite Framework Types, which is maintained bythe International Zeolite Association Structure Commission athttp://www.iza-structure.org/databases/, the member of which has beendesignated IM-5. As will be shown in detail, UZM-44 is different fromIM-5 in a number of its characteristics including its micropore volume.The instant microporous crystalline zeolite, UZM-44, has an empiricalcomposition in the as synthesized and anhydrous basis expressed by anempirical formula of:Na_(n)M_(m) ^(k+)T_(t)Al_(1-x)E_(x)Si_(y)O_(z)where “n” is the mole ratio of Na to (Al+E) and has a value fromapproximately 0.05 to 0.5, M represents a metal or metals selected fromthe group consisting of zinc, Group 1 (IUPAC 1), Group 2 (IUPAC 2),Group 3 (IUPAC 3), the lanthanide series of the periodic table, and anycombination thereof, “m” is the mole ratio of M to (Al+E) and has avalue from 0 to 0.5, “k” is the average charge of the metal or metals M,T is the organic structure directing agent or agents derived fromreactants R and Q where R is an A,Ω-dihalogen substituted alkane having5 carbon atoms and Q is at least one neutral monoamine having 6 or fewercarbon atoms, “t” is the mole ratio of N from the organic structuredirecting agent or agents to (Al+E) and has a value of from 0.5 to 1.5,E is an element selected from the group consisting of gallium, iron,boron and combinations thereof, “x” is the mole fraction of E and has avalue from 0 to about 1.0, “y” is the mole ratio of Si to (Al+E) andvaries from greater than 9 to about 25 and “z” is the mole ratio of O to(Al+E) and has a value determined by the equation:z=(n+k·m+3+4·y)/2Where M is only one metal, then the weighted average valence is thevalence of that one metal, i.e. +1 or +2. However, when more than one Mmetal is present, the total amount of:M _(m) ^(k+) =M _(m1) ^((k1)+) +M _(m2) ^((k2)+) +M _(m3) ^((k3)+) +M_(m4) ^((k4)+)+ . . .and the weighted average valence “k” is given by the equation:

$k = \frac{{m\;{1 \cdot k}\; 1} + {m\;{2 \cdot k}\; 2} + {m\;{3 \cdot k}\; 3\mspace{14mu}\ldots}}{{m\; 1} + {m\; 2} + {m\; 3\mspace{14mu}\ldots}}$

In one embodiment, the microporous crystalline zeolite, UZM-44, issynthesized by a hydrothermal crystallization of a reaction mixtureprepared by combining reactive sources of sodium, organic structuredirecting agent or agents T, aluminum, silicon, and optionally E, M, orboth. The reaction mixture does not comprise seeds of a layered materialL. The sources of aluminum include but are not limited to aluminumalkoxides, precipitated aluminas, aluminum metal, aluminum hydroxide,sodium aluminate, aluminum salts and alumina sols. Specific examples ofaluminum alkoxides include, but are not limited to aluminum sec-butoxideand aluminum ortho isopropoxide. Sources of silica include but are notlimited to tetraethylorthosilicate, colloidal silica, precipitatedsilica and alkali silicates. Sources of sodium include but are notlimited to sodium hydroxide, sodium bromide, sodium aluminate, andsodium silicate.

T is the organic structure directing agent or agents derived fromreactants R and Q where R is an A,Ω-dihalogen substituted alkane having5 carbon atoms and Q comprises at least one neutral monoamine having 6or fewer carbon atoms. R may be an A,Ω-dihalogen substituted alkanehaving 5 carbon atoms selected from the group consisting of1,5-dichloropentane, 1,5-dibromopentane, 1,5-diiodopentane, andcombinations thereof. Q comprises at least one neutral monoamine having6 or fewer carbon atoms such as 1-ethylpyrrolidine, 1-methylpyrrolidine,1-ethylazetidine, 1-methylazetidine, triethylamine, diethylmethylamine,dimethylethylamine, trimethylamine, dimethylbutylamine,dimethylpropylamine, dimethylisopropylamine, methylethylpropylamine,methylethylisopropylamine, dipropylamine, diisopropylamine,cyclopentylamine, methylcyclopentylamine, hexamethyleneimine. Q maycomprise combinations of multiple neutral monoamines having 6 or fewercarbon atoms.

M represents at least one exchangeable cation of a metal or metals fromGroup 1 (IUPAC 1), Group 2 (IUPAC 2), Group 3 (IUPAC 3) or thelanthanide series of the periodic table and or zinc. Specific examplesof M include but are not limited to lithium, potassium, rubidium,cesium, magnesium, calcium, strontium, barium, zinc, yttrium, lanthanum,gadolinium, and mixtures thereof. Reactive sources of M include, but arenot limited to, the group consisting of halide, nitrate, sulfate,hydroxide, or acetate salts. E is an element selected from the groupconsisting of gallium, iron, boron and combinations thereof, andsuitable reactive sources include, but are not limited to, boric acid,gallium oxyhydroxide, gallium nitrate, gallium sulfate, ferric nitrate,ferric sulfate, ferric chloride and mixtures thereof.

The reaction mixture containing reactive sources of the desiredcomponents can be described in terms of molar ratios of the oxides bythe formula:a-bNa₂O:bM_(n/2)O:cRO:dQ:1−eAl₂O₃ :eE₂O₃ :fSiO₂ :gH₂Owhere “a” has a value of about 10 to about 30, “b” has a value of 0 toabout 30, “c” has a value of about 1 to about 10, “d” has a value ofabout 2 to about 30, “e” has a value of 0 to about 1.0, “f” has a valueof about 30 to about 100, “g” has a value of about 100 to about 4000.

The examples demonstrate specific orders of addition for the reactionmixture which leads to UZM-44. However, as there are at least 6 startingmaterials, many orders of addition are possible. Also, if alkoxides areused, it is preferred to include a distillation or evaporative step toremove the alcohol hydrolysis products. While the organic structuredirecting agents R and Q can be added separately or together to thereaction mixture at a number of points in the process, it is preferredto mix R and Q together at room temperature and add the combined mixtureto a cooled mixture of reactive Si, Al and Na sources maintained at0-10° C. Alternatively, the mixture of R and Q, after mixing at roomtemperature, could be cooled and the reactive sources of Si, Al, and Naadded to the organic structure directing agent mixture while maintaininga temperature of 0-10° C. In an alternative embodiment, the reagents Rand Q could be added, separately or together, to the reaction mixture atroom temperature

The reaction mixture is then reacted at a temperature of about 160° C.to about 180° C., or about 165° C. to about 175° C., for a period ofabout 1 day to about 3 weeks and preferably for a time of about 3 daysto about 14 days in a stirred, sealed reaction vessel under autogenouspressure. Static crystallization does not yield UZM-44. Aftercrystallization is complete, the solid product is isolated from theheterogeneous mixture by means such as filtration or centrifugation, andthen washed with deionized water and dried in air at ambient temperatureup to about 100° C.

The as-synthesized UZM-44 is characterized by the x-ray diffractionpattern, having at least the d-spacings and relative intensities setforth in Table A below. Diffraction patterns herein were obtained usinga typical laboratory powder diffractometer, utilizing the K_(α) line ofcopper; Cu K alpha. From the position of the diffraction peaksrepresented by the angle 2theta, the characteristic interplanardistances d_(hkl) of the sample can be calculated using the Braggequation. The intensity is calculated on the basis of a relativeintensity scale attributing a value of 100 to the line representing thestrongest peak on the X-ray diffraction pattern, and then: very weak(vw) means less than 5; weak (w) means less than 15; medium (m) means inthe range 15 to 50; strong (s) means in the range 50 to 80; very strong(vs) means more than 80. Intensities may also be shown as inclusiveranges of the above. The X-ray diffraction patterns from which the data(d spacing and intensity) are obtained are characterized by a largenumber of reflections some of which are broad peaks or peaks which formshoulders on peaks of higher intensity. Some or all of the shoulders maynot be resolved. This may be the case for samples of low crystallinity,of particular coherently grown composite structures or for samples withcrystals which are small enough to cause significant broadening of theX-rays. This can also be the case when the equipment or operatingconditions used to produce the diffraction pattern differ significantlyfrom those used in the present case.

The X-ray diffraction pattern for UZM-44 contains many peaks; an exampleof the x-ray diffraction patterns for an as-synthesized UZM-44 productis shown in FIG. 1. Those peaks characteristic of UZM-44 are shown inTable A. Additional peaks, particularly those of very weak intensity,may also be present. All peaks of medium or higher intensity present inUZM-44 are represented in Table A.

The zeolite may be further characterized by the x-ray diffractionpattern having at least the d-spacings and intensities set forth inTable A.

TABLE A 2-Theta d(

) I/Io % 7.72 11.45 m 8.88 9.95 m 9.33 9.47 m 12.47 7.09 w-m 12.85 6.88vw 14.62 6.05 vw-w 15.27 5.80 w 15.57 5.68 w 16.60 5.34 w 17.70 5.04vw-w 18.71 4.74 w-m 19.30 4.59 w 22.55 3.94 m 23.03 3.86 vs 23.39 3.80 s24.17 3.68 m 25.01 3.56 m 26.19 3.40 vw-w 26.68 3.34 w-m 28.76 3.10 w-m30.07 2.97 w 35.72 2.51 vw-w 45.08 2.01 w 45.83 1.98 vw-w 46.77 1.94vw-w

As will be shown in detail in the examples, the UZM-44 material isthermally stable up to a temperature of at least 600° C. and in anotherembodiment, up to at least 800° C. Also as shown in the examples, theUZM-44 material may have a micropore volume as a percentage of totalpore volume of less than 60%.

Characterization of the UZM-44 product by high-resolution scanningelectron microscopy shows that the UZM-44 forms in lathes which assembleinto rectangular rod colonies.

As synthesized, the UZM-44 material will contain some exchangeable orcharge balancing cations in its pores. These exchangeable cations can beexchanged for other cations, or in the case of organic cations, they canbe removed by heating under controlled conditions. It is also possibleto remove some organic cations from the UZM-44 zeolite directly by ionexchange. The UZM-44 zeolite may be modified in many ways to tailor itfor use in a particular application. Modifications include calcination,ion-exchange, steaming, various acid extractions, ammoniumhexafluorosilicate treatment, or any combination thereof, as outlinedfor the case of UZM-4M in U.S. Pat. No. 6,776,975 B1 which isincorporated by reference in its entirety. Conditions may be more severethan shown in U.S. Pat. No. 6,776,975. Properties that are modifiedinclude porosity, adsorption, Si/Al ratio, acidity, thermal stability,and the like.

After calcination, ion-exchange and calcination and on an anhydrousbasis, the microporous crystalline zeolite UZM-44 has athree-dimensional framework of at least AlO₂ and SiO₂ tetrahedral unitsand an empirical composition in the hydrogen form expressed by anempirical formula ofM1_(a) ^(N+)Al_((1-x))E_(x)Si_(y′)O_(z″)where M1 is at least one exchangeable cation selected from the groupconsisting of alkali, alkaline earth metals, rare earth metals, ammoniumion, hydrogen ion and combinations thereof, “a” is the mole ratio of M1to (Al+E) and varies from about 0.05 to about 50, “N” is the weightedaverage valence of M1 and has a value of about +1 to about +3, E is anelement selected from the group consisting of gallium, iron, boron, andcombinations thereof, x is the mole fraction of E and varies from 0 to1.0, y′ is the mole ratio of Si to (Al+E) and varies from greater thanabout 9 to virtually pure silica and z″ is the mole ratio of O to (Al+E)and has a value determined by the equation:z″=(a·N+3+4·y′)/2

In the hydrogen form, after calcination, ion-exchange and calcination toremove NH₃, UZM-44 displays the x-ray diffraction pattern having atleast the d-spacings and intensities set forth in Table B. Those peakscharacteristic of UZM-44 are shown in Tables B. Additional peaks,particularly those of very weak intensity, may also be present. Allpeaks of medium or higher intensity present in UZM-44 are indicated inTable B.

TABLE B 2-Theta d(

) I/Io % 7.71 11.47 m-s 8.84 10.00 m-s 9.24 9.56 m 11.76 7.52 vw-w 12.467.10 m 14.38 6.15 vw 14.64 6.05 w 15.26 5.80 w 15.52 5.70 w-m 16.58 5.34w 17.72 5.00 w-m 18.64 4.76 w 22.56 3.94 w-m 23.06 3.85 vs 23.40 3.80 s24.12 3.69 m 25.06 3.55 m 26.16 3.40 vw-w 26.74 3.33 w-m 28.82 3.10 w30.12 2.96 vw-w 35.86 2.50 vw-w 45.32 2.00 w 46.05 1.97 vw-w 46.92 1.93vw-w

Similar to the as-synthesized material, the modified UZM-44 materialsare thermally stable up to a temperature of at least 600° C. and inanother embodiment, up to at least 800° C. and may have a microporevolume as a percentage of total pore volume of less than 60%.

Surface area, micropore volume and total pore volume may be determined,for example, by N₂ adsorption using the conventional BET method ofanalysis (J. Am. Chem. Soc., 1938, 60, 309-16) coupled with t-plotanalysis of the adsorption isotherm as implemented in Micromeritics ASAP2010 software. The t-plot is a mathematical representation ofmulti-layer adsorption and allows determination of the amount of N₂adsorbed in the micropores of the zeolitic material under analysis. Inparticular, for the materials described herein, points at 0.45, 0.50,0.55, 0.60, and 0.65 P/P₀ are used to determine the slope of the t-plotline, the intercept of which is the micropore volume. Total pore volumeis determined at 0.98 P/P₀. The UZM-44 of the instant invention has amicropore volume of less than 0.155 mL/g, typically less than 0.150mL/g, and often less than 0.145 mL/g. Additionally, by looking at thedV/d log D versus pore diameter plot (the differential volume ofnitrogen adsorbed as a function of pore diameter), as shown in FIG. 3,the UZM-44 of the instant invention contains no feature at around200-300 Å. As can be seen in FIG. 3, the material of Example 2, not inaccordance with the invention, does contain a feature at around 200-300Å. Instead, UZM-44 has an adsorption feature occurring at greater than450 Å. In an embodiment, greater than 0.1 mL N₂/gÅ is differentiallyadsorbed at a pore diameter of 475 Å. Preferably, greater than 0.1 mLN₂/gÅ is differentially adsorbed at pore diameters greater than 475 Åwhere differentially adsorbed indicates the differential volume ofnitrogen adsorbed at a particular pore diameter.

In specifying the proportions of the zeolite starting material oradsorption properties of the zeolite product and the like herein, the“anhydrous state” of the zeolite will be intended unless otherwisestated. The term “anhydrous state” is employed herein to refer to azeolite substantially devoid of both physically adsorbed and chemicallyadsorbed water.

The UZM-44 zeolite of this invention can also be used as a catalyst orcatalyst support in various hydrocarbon conversion processes.Hydrocarbon conversion processes are well known in the art and includecracking, hydrocracking, alkylation of aromatics or isoparaffins,isomerization of paraffins, olefins, or poly-alkylbenzenes such asxylene, trans-alkylation of poly-alkybenzene with benzene ormono-alkybenzene, disproportionation of mono-alkybenzene,polymerization, reforming, hydrogenation, dehydrogenation,transalkylation, dealkylation, hydration, dehydration, hydrotreating,hydrodenitrogenation, hydrodesulfurization, methanation and syngas shiftprocess. Specific reaction conditions and the types of feeds which canbe used in these processes are set forth in U.S. Pat. No. 4,310,440 andU.S. Pat. No. 4,440,871 which are hereby incorporated by reference.Preferred hydrocarbon conversion processes are those in which hydrogenis a component such as hydrotreating or hydrofining, hydrogenation,hydrocracking, hydrodenitrogenation, hydrodesulfurization, etc.

The zeolite as outlined above, or a modification thereof, may be in acomposite with commonly known binders. The UZM-44 is used as a catalystor catalyst support in various reactions. The UZM-44 preferably is mixedwith a binder for convenient formation of catalyst particles in aproportion of about 5 to 100 mass % UZM-44 zeolite and 0 to 95 mass-%binder, with the UZM-44 zeolite preferably comprising from about 5 to100 mass-% of the composite. The binder should preferably be porous,have a surface area of about 5 to about 800 m²/g, and be relativelyrefractory to the conditions utilized in the hydrocarbon conversionprocess. Non-limiting examples of binders are alumina, titania,zirconia, zinc oxide, magnesia, boria, silica-alumina, silica-magnesia,chromia-alumina, alumina-boria, aluminophosphates, silica-zirconia,silica, silica gel, and clays. Preferred binders are amorphous silicaand alumina, including gamma-, eta-, and theta-alumina, with gamma- andeta-alumina being especially preferred.

The UZM-44 zeolite with or without a binder can be formed into variousshapes such as pills, pellets, extrudates, spheres, etc. Preferredshapes are extrudates and spheres. Extrudates are prepared byconventional means which involves mixing of the composition eitherbefore or after adding metallic components, with the binder and asuitable peptizing agent to form a homogeneous dough or thick pastehaving the correct moisture content to allow for the formation ofextrudates with acceptable integrity to withstand direct calcination.The dough then is extruded through a die to give the shaped extrudate. Amultitude of different extrudate shapes are possible, including, but notlimited to, cylinders, cloverleaf, dumbbell and symmetrical andasymmetrical polylobates. It is also within the scope of this inventionthat the extrudates may be further shaped to any desired form, such asspheres, by any means known to the art.

Spheres can be prepared by the well known oil-drop method which isdescribed in U.S. Pat. No. 2,620,314 which is incorporated by reference.The method involves dropping a mixture of zeolite, and for example,alumina sol, and gelling agent into an oil bath maintained at elevatedtemperatures. The droplets of the mixture remain in the oil bath untilthey set and form hydrogel spheres. The spheres are then continuouslywithdrawn from the oil bath and typically subjected to specific agingtreatments in oil and an ammoniacal solution to further improve theirphysical characteristics. The resulting aged and gelled particles arethen washed and dried at a relatively low temperature of about 50 toabout 200° C. and subjected to a calcination procedure at a temperatureof about 450 to about 700° C. for a period of about 1 to about 20 hours.This treatment effects conversion of the hydrogel to the correspondingalumina matrix.

Hydrocracking conditions typically include a temperature in the range ofabout 204° C. to about 649° C. (400° to 1200° F.) or about 316° C. toabout 510° C. (600° F. and 950° F.). Reaction pressures are in the rangeof atmospheric to about 24,132 kPa g (3,500 psig), or between about 1379to about 20,685 kPa g (200 to 3000 psig). Contact times usuallycorrespond to liquid hourly space velocities (LHSV) in the range ofabout 0.1 hr⁻¹ to 15 hr⁻¹, preferably between about 0.2 and 3 hr⁻¹.Hydrogen circulation rates are in the range of 178 to about 8,888 std.m³/m³ (1,000 to 50,000 standard cubic feet (scf) per barrel of charge),or about 355 to about 5,333 std. m³/m³ (about 2,000 to about 30,000 scfper barrel of charge). Suitable hydrotreating conditions are generallywithin the broad ranges of hydrocracking conditions set out above.

The reaction zone effluent is normally removed from the catalyst bed,subjected to partial condensation and vapor-liquid separation and thenfractionated to recover the various components thereof. The hydrogen,and if desired some or all of the unconverted heavier materials, arerecycled to the reactor. Alternatively, a two-stage flow may be employedwith the unconverted material being passed into a second reactor.Catalysts of the subject invention may be used in just one stage of sucha process or may be used in both reactor stages.

Catalytic cracking processes are preferably carried out with the UZM-44composition using feedstocks such as gas oils, heavy naphthas,deasphalted crude oil residua, etc. with gasoline being the principaldesired product. Temperature conditions of about 454° C. to about 593°C. (about 850° F. to about 1100° F.), LHSV values of 0.5 to 10 andpressure conditions of from about 0 to about 344 kPa g (about 0 to 50psig) are suitable.

Alkylation of isoparaffins with olefins to produce alkylates suitable asmotor fuel components is carried out at temperatures of −30° to 40° C.,pressures from about atmospheric to about 6,895 kPa (1,000 psig) and aweight hourly space velocity (WHSV) of 0.1 to about 120. Details onparaffin alkylation may be found in U.S. Pat. No. 5,157,196 and U.S.Pat. No. 5,157,197, which are incorporated by reference.

Alkylation of aromatics usually involves reacting an aromatic (C₂ toC₁₂), especially benzene, with a monoolefin to produce an alkylsubstituted aromatic. The process is carried out at an aromatic:olefin(e.g., benzene:olefin) ratio of between 1:1 and 30:1, a olefin LHSV ofabout 0.3 to about 10 hr⁻¹, a temperature of about 100° to about 250° C.and pressures of about 1379 kPa g to about 6895 kPa g (about 200 toabout 1000 psig). Further details on apparatus may be found in U.S. Pat.No. 4,870,222 which is incorporated by reference.

Dealkylation of aromatics usually involves passing an alkyl substitutedaromatic, especially ethylbenzene or toluene, over a catalytic compositeto produce an olefin and a dealkylated aromatic, especially benzene.Typically, the olefin is hydrogenated to yield a paraffin. Additionalexamples of dealkylation of aromatics include the dealkylation ofmethylethylbenzene (ethyltoluene) to toluene, ethylbenzene, and/orbenzene and the dealkylation of isopropylmethylbenzene (cumene) totoluene, isopropylbenzene (cumene), and/or benzene. Typical dealkylationconditions include a temperature in the range from about 100° to about600° C. and pressure from 10 kPa to about 5 MPa. The LHSV is from about0.1 to about 50 hr⁻¹. The hydrocarbon contacts the catalyst in admixturewith a gaseous hydrogen-containing stream in a line at ahydrogen-to-hydrocarbon mole ratio of from about 0.1:1 to 15:1 or more,and preferably a ratio of from about 0.1 to 10. Further details onapparatus may be found in U.S. Pat. No. 8,134,037 which is herebyincorporated by reference.

Methylaromatic formation is an alternative process to generate tolueneand xylenes from benzene and a paraffin source having at least oneparaffin having from 2 to about 6 carbon atoms, referred to herein as aC2-C6 paraffin source. In another embodiment, a paraffin sourcecomprising at least one paraffin having from 3 to about 6 carbon atoms,may be used. The reactions involved may include cracking, aromaticalkylation, and transalkylation.

The C2-C6 paraffin source can include at least one of, independently,one or more cycloalkanes and alkanes, and may comprise at least about5%, by weight, of the feed. Optionally, the paraffin source may alsoinclude one or more olefins. The cycloalkane preferably has at leastthree, and desirably five, carbon atoms in the ring. The feed mayinclude at least about 10%, by weight, one or more cycloalkanes, orabout 10-about 70%, by weight, one or more cycloalkanes with respect tothe weight of the feed. Moreover, the feed may include up to about 50%,by weight, of one or more C2-C6 hydrocarbons with respect to the weightof the feed. Usually, the feed is substantially absent of methylatingagents containing one or more hetero-atoms. As an example, the feed canhave less than about 1%, preferably less than about 0.1%, by weight, ofone or more methylating agents.

Typically, the feed can include aromatic compounds as well. The aromaticcompounds can include benzene, toluene, one or more xylenes,naphthalene, ethylbenzene, and one or more polynuclear aromatics. In anembodiment, benzene is preferred. Typically, the feed can comprise about20-about 95%, by weight, of one or more aromatics, such as benzene, withrespect to the weight of the feed. In some other embodiments, thebenzene content of the feed can be about 15-about 25%, by weight, withrespect to the weight of the feed.

The reaction zone in which the C2-C6 paraffin source and aromaticcompound are reacted over the UZM-44 catalytic composite can operateunder any suitable conditions in the liquid or gas phase, however gasphase reaction is preferred to facilitate the cracking of C2-C6 alkanes.Particularly, the reaction zone can operate at a temperature of about250-about 700° C., preferably about 350-about 600° C., a pressure ofabout 100-about 21,000 kPa, preferably about 1,379-about 6,895 kPa, anda weight hourly space velocity (WHSV) of about 0.1-about 100 hr⁻¹,preferably about 2-about 10 hr⁻¹. The feed can also contact the catalystin admixture with a gaseous hydrogen-containing stream in a line at ahydrogen-to-hydrocarbon mole ratio of from about 0:1 to 5:1, andpreferably a ratio of from about 0 to 1.

Additional processes and processing conditions where the catalyticcomposite UZM-44 may be employed are discussed in US 20110178356, US20110178354, and US 20110174692, each of which are hereby incorporatedby reference in their entirety.

Generally, a downstream process can utilize one or more products, suchas benzene, para-xylene, meta-xylene and ortho-xylene, of theembodiments disclosed herein. Particularly, para-xylene, upon oxidation,can yield terephthalic acid used in the manufacture of textiles, fibers,and resins. Moreover, para-xylene can be used as a cleaning agent forsteel and silicon wafers and chips, a pesticide, a thinner for paint,and in paints and varnishes. Meta-xylene can be used as an intermediateto manufacture plasticizers, azo dyes, wood preservatives and other suchproducts. Ortho-xylene can be a feedstock for phthalic anhydrideproduction. Additionally, xylenes generally may be used as a solvent inthe printer, rubber, and leather industries. Moreover, the methyl groupson xylenes can be chlorinated for use as lacquer thinners. Benzene canbe used as a feed to make cyclohexane, which in turn may be used to makenylons. Also, benzene can be used as an intermediate to make styrene,ethylbenzene, cumene, and cyclohexane among other products.

The following examples are presented in illustration of this inventionand are not intended as undue limitations on the generally broad scopeof the invention as set out in the appended claims.

The structure of the UZM-44 zeolite of this invention was determined byx-ray analysis. The x-ray patterns presented in the following exampleswere obtained using standard x-ray powder diffraction techniques. Theradiation source was a high-intensity, x-ray tube operated at 45 kV and35 ma. The diffraction pattern from the copper K-alpha radiation wasobtained by appropriate computer based techniques. Flat compressedpowder samples were continuously scanned at 2° to 56° (2θ). Interplanarspacings (d) in Angstrom units were obtained from the position of thediffraction peaks expressed as θ where θ is the Bragg angle as observedfrom digitized data. Intensities were determined from the integratedarea of diffraction peaks after subtracting background, “I_(o)” beingthe intensity of the strongest line or peak, and “I” being the intensityof each of the other peaks.

As will be understood by those skilled in the art the determination ofthe parameter 2θ is subject to both human and mechanical error, which incombination can impose an uncertainty of about ±0.4° on each reportedvalue of 2θ. This uncertainty is, of course, also manifested in thereported values of the d-spacings, which are calculated from the 2θvalues. This imprecision is general throughout the art and is notsufficient to preclude the differentiation of the present crystallinematerials from each other and from the compositions of the prior art. Insome of the x-ray patterns reported, the relative intensities of thed-spacings are indicated by the notations vs, s, m, w and vw whichrepresent very strong, strong, medium, weak, and very weak respectively.In terms of 100×I/I_(o), the above designations are defined as:vw=<5;w=6-15;m=16-50:s=51-80; and vs=80-100

In certain instances the purity of a synthesized product may be assessedwith reference to its x-ray powder diffraction pattern. Thus, forexample, if a sample is stated to be pure, it is intended only that thex-ray pattern of the sample is free of lines attributable to crystallineimpurities, not that there are no amorphous materials present.

In order to more fully illustrate the invention, the following examplesare set forth. It is to be understood that the examples are only by wayof illustration and are not intended as an undue limitation on the broadscope of the invention as set forth in the appended claims.

Example 1

5.28 g of NaOH, (97%) was dissolved in 111.88 g water. 1.16 g Al(OH)₃,(29.32 wt.-% Al), was added to the sodium hydroxide solution. Upon themixture becoming a solution, 33.75 g Ludox AS-40 was added and thesolution was stirred vigorously for 1-2 hours and then cooled to 0°C.-4° C. Separately, 8.89 g 1,5-dibromopentane, (97%) was mixed with9.56 g 1-methylpyrrolidine, (97%) to form a second mixture. The secondmixture was added to the cooled mixture to create the final reactionmixture. The final reaction mixture was vigorously stirred andtransferred to a 300 cc stirred autoclave. The final reaction mixturewas digested at 170° C. for 120 hours with stirring at 100 rpm. Theproduct was isolated by filtration. The product was identified as UZM-44by XRD. Analytical results showed this material to have the followingmolar ratios, Si/Al of 11.77, Na/Al of 0.21, N/Al of 1.02, C/N of 7.75.The product generated by this synthesis was calcined under flowing airat 600° for 6 hours. It was then ion exchanged four times with 1 Mammonium nitrate solution at 75° C. followed by a calcination at 500° C.under air for 2 hours to convert NH₄ ⁺ into H⁺. Analysis for thecalcined, ion-exchanged sample shows 39.1% Si, 3.26% Al, 90 ppm Na witha BET surface area of 299 m²/g, pore volume of 0.239 cm³/g, andmicropore volume of 0.139 cm³/g.

Comparative Example 2

10.8 g of Aerosil 200 was added, while stirring, to a solution of 12.24g 1,5-bis(N-methylpyrrolidinium)pentane dibromide in 114 g H₂O. A verythick gel was formed. Separately, a solution was made from 60 g H₂O,3.69 g NaOH (99%), 0.95 g sodium aluminate (26.1% Al by analysis), and1.86 g NaBr (99%). This second solution was added to the above mixture.The final mixture was divided equally between 7 45 cc Parr vessels. Onevessel, which was digested for 12 days at 170° C. in a rotisserie ovenat 15 rpm, yielded a product which was determined by XRD as having theIMF structure. The product was isolated by filtration. Analyticalresults showed this material to have the following molar ratios, Si/Alof 12.12, Na/Al of 0.08, N/Al of 1.03, C/N of 7.43. The productgenerated by this synthesis was calcined under flowing air at 600° for 6hours. It was then ion exchanged four times with 1 M ammonium nitratesolution at 75° C. followed by a calcination at 500° C. under air for 2hours to convert NH₄ ⁺ into H⁺. Analysis for the calcined, ion-exchangedsample shows 38.8% Si, 2.99% Al, 190 ppm Na with a BET surface area of340 m²/g, pore volume of 0.260 cm³/g, and micropore volume of 0.160cm³/g.

Example 3

544 g of NaOH, (97%) was dissolved in 9.53 kg water. 118 g Al(OH)₃ wasadded to the sodium hydroxide solution while stirring. Of Ludox AS-40,3.83 kg was added and the solution was stirred vigorously for 2 hoursand then cooled to 0° C.-5° C. A solution containing 941 g H2O, 453 g1,5-dibromopentane and 325 g N-methylpyrrolidine was added to the cooledmixture to create the final reaction mixture. The final reaction mixturewas vigorously stirred and transferred to a 5 gallon stirred autoclavebefore digestion at 160° C. for 11 days. The product was isolated byfiltration. The product was identified as UZM-44 by XRD. Analyticalresults showed this material to have the following molar ratios, Si/Alof 11.77, Na/Al of 0.21, N/Al of 1.02, C/N of 7.75. The productgenerated by this synthesis was calcined under flowing air at 600° for 6hours. Analysis for the calcined sample shows a BET surface area of 301m²/g, pore volume of 0.238 cm³/g, and micropore volume of 0.142 cm³/g.

Example 4

A UZM-44 in the H+ form was loaded into a vertical steamer. The UZM-44was exposed to 100% steam at 725° C. for 12 hours or 24 hours. Thestarting UZM-44 had a BET surface area of 340 m²/g, pore volume of 0.301cm³/g, and micropore volume of 0.154 cm³/g. After 12 hours of steaming,the UZM-44 was still identified as UZM-44 by XRD though the intensity ofthe first 3 peaks had increased to very strong, very strong—strong, andvery strong—strong respectively. All other peaks were at positions andintensities described in Table B. The material had a BET surface area of274 m²/g, pore volume of 0.257 cm³/g, and micropore volume of 0.127cm³/g. After 24 hours of steaming, the UZM-44 was still identified asUZM-44 by XRD though the intensity of the first 3 peaks had increased tovery strong, very strong—strong, and very strong—strong respectively.All other peaks were at positions and intensities described in Table B.The material had a BET surface area of 276 m²/g, pore volume of 0.262cm³/g, and micropore volume of 0.128 cm³/g.

Example 5

UZM-44 was synthesized from a gel of composition 1 Al₂O₃:43.6 SiO₂:11.6Na₂O:6.52 1,5-dibromopentane:18.95 N-methylpyrrolidine:1321 H₂O bydissolving NaOH in water and then liquid sodium aluminate was added tothe sodium hydroxide solution. Ultrasil VN3 was then added as the silicasource followed by 1,5-dibromopentane and N-methylpyrrolidine to formthe final reaction mixture. The final reaction mixture was vigorouslystirred and transferred to a 2 L stirred autoclave. The final reactionmixture was digested at 50° C. for 24 h then at 160° C. for 12 dayswhile stirring. The product was isolated by filtration. The product wasidentified as UZM-44 by XRD. The product generated by this synthesis wascalcined under flowing air at 600° for 6 hours. It was thenion-exchanged with 1 M ammonium nitrate solution.

Example 6

The product generated by the synthesis described in Example 1 was boundwith Al₂O₃ in a 75:25 weight ratio and extruded in ⅛″ cylinders to formUZM-44/Al₂O₃. The extrudates were then calcined using a 2° C./minuteramp to 550° C., holding for 3 hours and then cooling to roomtemperature. The 20 to 60 mesh fraction was isolated and then used asthe catalytic composite in a chemical reaction to form ethylbenzene andxylenes.

Benzene and propane were fed at a 2:1 mole ratio into a reactor at 400psig along with a hydrogen stream such that the hydrogen to hydrocarbonmole ratio was about 1.0. At 500° C. and 2.5WHSV, conversion of benzenewas 63 wt % and conversion of propane was 90 wt %. Yield of aromaticcompounds at these conditions included 25 wt % to toluene, 1 wt % toethylbenzene, 7 wt % to xylenes and 5% to C9 aromatics.

Example 7

250 mg of H⁺-UZM-44 was pressed and sieved to 40-60 mesh before loadinginto a catalytic test apparatus. The catalytic composite was heatedunder N₂ flow of 50 mL/min to 550° C. and held for 60 min. The apparatuswas then cooled to 400° C. before the feed was switched from N₂ to N₂saturated with toluene at the same flow rate. Toluene transalkylationwas performed at temperatures ranging from 400° C. to 550° C.

TABLE 1 UZM-44 Temperature Xylene Yield 400° C. 12.9 450° C. 15.5 500°C. 18.4 550° C. 19.2

The invention claimed is:
 1. A process for the alkylation of aromaticscomprising contacting a feed comprising at least a first aromaticcompound and an olefin with a microporous crystalline zeolitic catalyticcomposite at hydrocarbon conversion conditions to produce at least asecond aromatic, wherein the second aromatic is at least one linearalkyl substituted aromatic, the catalytic composite comprising amicroporous crystalline zeolite, UZM-44-Modified, having athree-dimensional framework of at least AlO₂ and SiO₂ tetrahedral unitsand an empirical composition in the hydrogen form expressed by anempirical formula ofM1_(a) ^(N+)Al_((1-x))E_(x)Si_(y′)O_(z″) where M1 is at least oneexchangeable cation selected from the group consisting of alkali,alkaline earth metals, rare earth metals, ammonium ion, hydrogen ion andcombinations thereof, “a” is the mole ratio of M1 to (Al+E) and variesfrom about 0.05 to about 50, “N” is the weighted average valence of M1and has a value of about +1 to about +3, E is an element selected fromthe group consisting of gallium, iron, boron, and combinations thereof,x is the mole fraction of E and varies from 0 to 1.0, y′ is the moleratio of Si to (Al+E) and varies from greater than about 9 to virtuallypure silica and z″ is the mole ratio of O to (Al+E) and has a valuedetermined by the equation:z″=(a·N+3+4·y′)/2 wherein the macroporous crystalline zeolite,UZM-44-Modified, is further characterized in that it has the x-raydiffraction pattern having at least the d-spacings and intensities setforth in Table B: TABLE B 2-Theta d(

) I/Io % 7.71 11.47 m-s 8.84 10.00 m-s 9.24 9.56 m 11.76 7.52 vw-w 12.467.10 m 14.38 6.15 vw 14.64 6.05 w 15.26 5.80 w 15.52 5.70 w-m 16.58 5.34w 17.72 5.00 w-m 18.64 4.76 w 22.56 3.94 w-m 23.06 3.85 vs 23.40 3.80 s24.12 3.69 m 25.06 3.55 m 26.16 3.40 vw-w 26.74 3.33 w-m 28.82 3.10 w-m30.12 2.96 w 35.86 2.50 vw-w 45.32 2.00 w 46.05 1.97 vw-w 46.92 1.93vw-w

and wherein the process is operated at an aromatic:olefin mole ratio ofbetween 5:1 and 30:1, a LHSV of about 0.3 to about 6 hr⁻¹, a temperatureof about 100° to about 250° C. and a pressures of about 200 to about1000 psig.
 2. The process of claim 1 wherein the microporous crystallinezeolitic catalytic composite is thermally stable up to a temperature ofgreater than 600° C.
 3. The process of claim 1 wherein the microporouscrystalline zeolitic catalytic composite has a micropore volume as apercentage of total pore volume of less than 60%.
 4. The process ofclaim 1 wherein the microporous crystalline zeolitic catalytic compositehas micropore volume of less than 0.155 mL/g.
 5. The process of claim 1wherein the microporous crystalline zeolitic catalytic composite hasmicropore volume of less than 0.150 mL/g.
 6. The process of claim 1wherein the microporous crystalline zeolitic catalytic compositeexhibits no feature at 200-300 Å on a dV/d log D versus pore diameterplot of differential volume of nitrogen adsorbed as a function of porediameter.
 7. The process of claim 1 wherein the microporous crystallinezeolitic catalytic composite exhibits adsorption occurring at greaterthan 450 Å on a dV/d log D versus pore diameter plot of differentialvolume of nitrogen adsorbed as a function of pore diameter.
 8. Theprocess of claim 1 wherein the differential volume of nitrogen adsorbedby the catalytic composite at a pore diameter of 475 Å is greater than0.1 mL N₂/gÅ on a dV/d log D versus pore diameter plot of differentialvolume of nitrogen adsorbed as a function of pore diameter.
 9. Theprocess of claim 1 wherein the differential volume of nitrogen adsorbedby the catalytic composite at pore diameters greater than 475 Å isgreater than 0.1 mL N₂/gÅ on a dV/d log D versus pore diameter plot ofdifferential volume of nitrogen adsorbed as a function of pore diameter.10. The process of claim 1 wherein the first aromatic is benzene. 11.The process of claim 1 further comprising removing an effluentcomprising the second aromatic, fractionating the effluent, andrecovering the second aromatic.
 12. The process of claim 11 furthercomprising, subjecting the effluent to partial condensation andvapor-liquid separation prior to fractionation.
 13. The process of claim11 further comprising recycling at least a portion of the effluent tothe catalyst.
 14. The process of claim 1 wherein the catalytic compositeis located in one or more catalyst zones arranged in series or parallelconfiguration, and wherein the catalytic composite may be in fixed bedsor fluidized beds.